Condensation products of sugar acid lactones with aryl halides



CONDENSATION PRODUCTS F 'SUGAR AClD LACTONES ARYL HALIDES Carl B. Linn,Riverside, and Jerome A. Vesely, Park Ridge, 111., assignors, by mesneassignments, to Universal Oil Products Company, Des Plaines, 11]., acorporation of Delaware No Drawing. Filed May 9, 1957, Ser. No. 658,00316 Claims. (Cl. 260 -3436) the products or novel compositions of matterformed by' said condensation. The organic products formed by ourcondensation of sugar acid lactones with aryl halides are useful per se,and are also useful as intermediates in the manufacture of detergents,pharmaceuticals, surface coatings, resins, gelling agents, and the like.For example, the lactone of 1,1-di-chlorophenyl-l-desoxy-glucuronicacid, formed by the condensation of glucuronolactone with chlorobenzene,can be converted into a so-called sugar detergent by ester exchange withmethyl laurate, methyl myn'state, methyl palmitate, methyl oleate, ormethyl stearate. These ester exchange reactions, as described inIndustrial & Engineering .Chemistry 48, 1459- 1464 (1956), arepreferably carried out in dimethylformamide solution utilizin potassiumcarbonate or sodium methoxide as the catalysts. As is observable fromthis publication, the preparation of detergents from sugar derivativesmay be carried out readily by one skilled in the art.

More specifically, this invention relates to a process for producinghaloaryl-substituted polyhydroxy carboxylic acids, and salts andlactones thereof. These lactones are internal esters of said polyhydroxycarboxylic acids, formed by the loss of Water by interaction of ahydroxyl group with the carboxylic acid group of a given molecule of apolyhydroxy carboxylic acid, with the resultant formation of furanose orpyranose ring systems or lactones.

An object of this invention is to condense an aryl halide with a lactoneof a sugar acid in the presence of a Fn'edel-Crafts metal halidecatalyst, and to recover the products of said condensation.

Another object of this invention is to condense. an aryl halide withglucuronolactone, and to recover the product of said condensation.

A still further object of this invention is to condense chlorobenzenewith glucuronolactone, and to recover the product of said condensation.

One embodiment of this invention relates to a process which comprisescondensing an aryl halide with a lactone of a sugar acid in the presenceof a Friedel-Crafts metal halide catalyst, and recovering the resultantcondensation product.

Another embodiment of this invention relates to a process whichcomprises condensing an aryl halide with a lactone of a sugar acid inthe presence of an aluminum chloride catalyst, and recovering theresultant condensa tion product.

Still another embodiment of this invention relates to a process whichcomprises condensing chlorobenzene with glucuronolactone in the presenceof an aluminum" chlo- 2,938,912 Patented May 31 1960 ice ride catalyst,and recovering the resultant condensation product.

A still further embodiment of this invention is a product produced bycondensing chlorobenzene with glucu ronolactone in the presence ofaluminum chloride.

A still further embodiment of this invention is a member of the groupconsisting of a haloaryl-l-desoxy-alduronolactone, ahaloaryl-l-desoxy-alduronic acid, and a sodium salt of ahaloaryl-l-desoxy-alduronicacid.

We have found that useful water-soluble and waterinsoluble condensationproducts are formed by reacting lactones of sugar acids with arylhalides in the presence of Friedel-Crafts metal halide catalysts, andparticularly in the presence of aluminum chloride. These condensationreactions are carried out conveniently in ordinary glass alkylationequipment using temperatures of from about -20 C. to about 150 C., andpreferably at tem-f peratures of from about 20 C. to about C. While manyof the condensation reactions are carried out at substantiallyatmospheric pressure, it may be desirable in certain instances and withcertain reactants to carry out the reaction in metal autoclaves atpressures up to 100 atmospheres or more. It is convenient in most imstances to operate the equipment utilized at the pressure generated bythe reaction mixture and catalyst contained therein at the temperatureutilized.

Aryl halides suitable for use as starting materials in the process ofthis invention include. the halogen deriva-{ tives of aromatichydrocarbons in which there is retained at least one hydrogen atomattached to a carbon atom of the aromatic nucleus. Thus compounds suchas hexachlorobenzene are excluded from the scope of the process of thepresent invention, since such compounds are inoperative. Aryl halidesutilizable within the broad scope of' the process of the presentinvention include fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, 0rtho-chl0r0toluene,' meta-chlorotoluene, parachlorotoluene,ortho-bromotoluene, meta-bromotoluene, para-bromotoluene,ortho-bromoanisole, para-bromoanisole, para-bromodimethylaniline,.ortho-dichlorobenzene, para-dichlor'obenzene, 1,2,4-trichlorobenzene,1,2,3,4-tet rachlorobenzene, para dibromobenzene, orthobromochlorobenzene, para-bromochlorobenzene, ortho-bromoiodobenzene,para-bromoiodobenzene, ortho-chloroiodobenzene, para-chloroiodobenzene,etc. Of course, the above enumerated haloaromatic compounds are notnecessarily equivalent in the process of the present invention, and theconditions utilized for any particular one may be different from theconditions utilized with others. As stated hereinabove, of the arylhalides utilizable in the process of the present invention, aryl halideswhich are derivatives of aromatic hydrocarbons are preferred, and ofthese preferred aryl halides, those in which chlorine or brominereplaces one or more of nuclear hydrogen atoms of an aromatic ring of anaromatichydrocarbon are still more particularly preferred. However, asstated hereinabove, the resultant aryl halide derivative of an aromatichydrocarbon still contains at least one replaceable nuclear hydrogenatom. Such aryl halide derivatives of aromatic hydrocarbons include thechlorine or bromine derivatives of benzene, toluene, ortho-xylenc,meta-xylene, para-xylene, ethylbenzene, 1,2,3-trimethylbenzene, 1,2,4trimethylbenzene, ortho ethyltoluene, meta-ethyltoluene,para-ethyltoluene, n-propylbenzene, isopropylbenzene or cumene, butylbenzenes, amyl benzenes, and higher molecular Weight alkyl aromatichydrocarbons in which the halogen atoms are substituted for one or moreof the nuclear hydrogen atoms of the aromatic hydrocarbons but in whichresultant aryl halides there remains at least one nuclear hydrogen atomattached to a carbon atom of the aromatic nucleus. Other suitable arylhalides include the nuclear halogen derivatives of alkylaromatichydrocarbons with long chain alkyl groups, said alkylaromatichydrocarbons being produced by the alkylation of aromatic hydrocarbonswith olefin polymers to yield such materials as hexylbenzenes, hexyl-ttoluenes, nonylbenzenes, nonyltoluenes, dodecylbenzenes,dodecyltoluenes, etc. Often alkylate suitable for halogenation toproduce starting materials for the process of the present invention isobtained as a high boiling fraction in which the alkyl group attached tothe aromatic hydrocarbon nucleus may contain from about 6 to about 24carbon atoms. If any preference exists in the nuclear halogenated alkylaromatic hydrocarbons for use in the process of the present invention,it is to those halogenated alkyl aromatic hydrocarbons in which thealkyl group contains from about 1 to about 5 carbon atoms. Other arylhalides for conversion with sugar acid lactones into novel compositionsof matter include those with two or more aryl groups such as halogenateddiphenyl, halogenated diphenyl methane, halogenated triphenyl methane,etc. Examples of suitable utilizable aryl halides which containcondensed benzene rings'include chloronaphthalene, chloroanthracene,chlorophenanthrene, ch ronaphthacene, chlororubrene, etc.

The sugar acid lactones which are utilizable as starting materials inthe process of the present invention include both the alpha and betaforms of lyxuronolactone, xyluronolactone, arabinuronolactone,riburonolactone, taluronolactone, galacturonolactone, iduronolactone,guluronolactone, mannuronolactone, glucuronolactone, altruronolactone,alluronolactone, etc. These internal esters of alduronic acids arespontaneously formed upon heating suitable .alduronic acids in whichformation of a 1-4 or gamma-lactone structure is possible, or in whichformation of a 1-5 or delta-lactone structure is possible. The alduronicacids are a group of compounds which are obtainable by oxidation of theterminal alcohol group of aldoses. The penturonic acids and theirconversion to penturonolactones can be represented by the followinggeneral equation:

The hexuronic acids and their conversion to hexuronolactones can berepresented by the following general Since the alduronic acids mustcontain at least 5 car bon atoms to be able to form gamma-lactones, thesugar acid lactones which are preferred as starting materials in theprocess of this invention will contain at least 5 carbon atoms. Alsoutilizable are sugar acidvlactones containing 6 carbon atoms and more.When these sugar acid lactones react with the aryl halides to form thenew compositions of matter of the present invention, they do .so byreaction at the number 1 carbon atom, thus forming haloaryl derivativesof lactones of l-desoxy-uronic vacids.

As an example of this process, glucuronolactone may be reacted with anequimolecular proportion or less of chlorobenzene to give amono-(chlorophenyl)-desoxy- .rglucuronic acid lactone or with more thanan equirnolecular proportion of chlorobenzene to give the lactone ofdi-(chlorophenyl) desoxy --glucuronic acid. The structures of some ofthese haloaryl hexuronic acid lactone reaction products are representedas follows:

01 Cl Cl An example of our di-(haloaryl)-desoxyqhexuronie acid productsis 1,1-di-(chlorophenyl)-1-desoxy glucuronic acid represented by thefollowing structural formula:

C1 Cl 1 l-(p-bromophenyl)-l-desoxy-lyxuronolactone,

1,l-di-(p-bromophenyD-l-desoXy-lyxuronolactone,1-(p-bromophenyl)-l-desoxy-xyluronolactone,

l 1-di-(p-bromophenyl)-1-desoxy-xyluronolactone,

1- (p-bromophenyl) l-desoxy-arabinuronolactone,1,Ldi-(p-bromophenyl}1-desoxyarabinuronolactonml-(p-bromophenyD-1-desoxy-riburonolactone,1,l-di-(pabromophenyD-1-desoxy-riburonolactone,

l (p-bromophenyl)-l-desoxy-taluronolactone,

,1 di-(p-brornophenyl)-l-desoxy-taluronolactone, v

1-(3,4-dischlorophenylJ-l-desoxy-manmironic acid,

l,l-di-(3,4-dichlorophenyl) -l-desoxy-mannuronic acid,

1-(3,4-dichlorophenyl)-1-desox -glucuronic acid,

1,l-di-(3,4-dichlofophenyl)-1-desoXy-glucuronic acid,

1(3,4-dichlor ophenyl)-l-desoxy-altruronic acid,

1,l-di-(3,4-dichlorophenyl)-1-desoXy-altruronic acid, 7

1-(3,4-dichlorophenyl) -1-desoXy-alluronic acid,

1,1-di-(3,4 dichlorophenyl)-l-desoXy-alluronic acid,

the sodium salt of l-(p-chlorophenyl)-1-desoXy-lyxuronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-l-desoxylyxuronic acid,

the sodium salt of l-(p-chlorophenyl)-1-desoxy-xyluronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-1-desoxyxyluronic acid,

the sodium' salt of l-(p-chlorophenyl)-1-desoXy-arahinu- Ionic acid,

the sodium salt of l-(p-chlorophenyl)-1-desoxy-arabinuronic acid,

the sodium salt of l-(p-chlorophenyl)-1-desoxy-riburonic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-1-desoxyriburonic acid,

the sodium salt of l-(p-chlorophenyl)-l-desoxy-taluronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-1-desoxy-taluronic acid,

the sodium salt of l-(p-chlorophenyl)-ldesoxy-galacturonic acid,

the sodium salt of 1,1-di-(p-cl1lorophenyl)-1-desoxygalacturonic acid,

the sodium salt of l-(p-chlorophenyl)-l-desoxy-iduronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-l-desoxyiduronic acid,

the sodium salt of l-(p-chlorophenyl)-l-desoxy-gulutonic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-l-desoxygulurom'c acid,

the sodium salt of l-(p-chlorophenyl)-1-desoxy-mannuronic acid,

the sodium salt of l,l-di-(p-chlorophenyl)-l-desoxymannuronic acid,

the sodium salt of l-(p-chloi'opheuyl)-l-desoXy-glucuronic acid,

the sodium salt of l,l-di-(pchlorophenyl)-l-desoxyglucuronic acid,

the sodium salt of l -(p-chlorophenyl)-l-desoXy-altruronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)-l-desoxy-altruronic acid,

the sodium salt of l-(p-chlorophenyl)-l-desoxy-alluronic acid,

the sodium salt of 1,1-di-(p-chlorophenyl)l-desoxy-alluronic acid,

the sodium salt acid,

the sodium salt of 1,l-di-(p-bromophenyl)-1-desoxylyxuronic acid,

the sodium salt of l-(p-bromophenyl)-1-desoxy-xyluronic acid,

the sodium salt of 1,1-di-(pbromophenyl)-1-desoxyxyluronic acid,

the sodium salt of l-(p-bromophenyl)-l-desoXy-arabinurouicacid,

of 1(p-bromophenyl)-1-desoxy-lyxuronic the sodium salt of1,1-di-(p-brcmophenyl)-l-desoxyarabinuronic acid,

the sodium salt of l-(p-bromophenyl)-l-desoxy-riburonic acid,

the sodium salt of 'l,l-di-(p-bromophenyl)-l-desoxyributonic acid,

the sodiumsalt of l-(p-bromophenyl)-1-desoxy-taluronic acid;

the sodium salt of 1,1-di- (p-bromophenyl) l desoxyetalu Ionic acid,

the sodium salt of l-(p-bromophenyl)-1-desoxy-galactu I'ODiC acid, i

the sodium salt of 1,1-di-(p-b1omophenyl)-1desoXy galacturonic-acid,

the sodium salt of 1-(p-bromophe'nyl)-l-desoxy-iduronic acid, 4

the sodium salt of 1,l--di-(p-bromophenyl)-l-desoxyiduronic acid,

the sodium salt of 'l-(p-bromophenyl)-1-desoxy-guluronic acid,

the sodium salt of 1,1-di-(p-bromophenyl)-l-desoxyguluronic acid, a

the sodium salt of l-(p-bromophenyl)-l-desoxy mannu- Ionic acid, I

the sodium salt of 1,1-di-(p-hromophenyl)-1-desoxy mannuronic acid,

the sodium salt of 1-(p-bromophenyl)-1-desoxy-glucuronic acid,

the sodium salt of 1,1-di-(p-bromophenyl)-1-desoXyglucuronic acid,

the sodium salt of 'l-(p-bromophenyl)-1-desoxy-altruronic acid,

the sodium salt of 1,l-di-(p-bromophenyl)-l-desoxy-altruronic acid,

the sodium salt of l-(p-bromophenyl)-1-desoxy-alluronic acid,

the sodium salt of l,1-di-(p-bromophenyl) -1-desoxyalluronic acid,

the sodium salt of 1-(2,5-dichlorophenyl)-1-desoxylyxuronic acid,

the sodium salt of 1,l-di-(2,5-dichlorophenyl)-l-desoxylyxuronic acid,

the sodium salt of 1-(2,5-dichlorophenyl)-1-desoxyxyluronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-1-desoxyxyluronic acid, v

the sodium salt of 1-(2,5-dichlorophenyl)-l-desoxy-arabinuronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-l-desoxyarabinuronicacid,

the sodium salt of 1-(2,5-dichlorophenyl)-1-desoxyriburonic acid,

the sodium salt of 1,l-di-(2,5-dichlorophenyl)-1-desoxyriburonic acid,

the sodium salt of l-(2,5-dichlorophenyl)-1-desoxy-talu- Ionic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-1-desoxytaluronic acid,

the sodium salt of l-(2,5-dichlorophenyl)-1-desoxygalacturonic acid,

the sodium salt of 1,l-di-(2,5-dichlorophenyl)-1-desoxygalacturonicacid,

the sodium salt of 1-(2,5-dichlorophenyl)-1-desoxyiduronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-1-desoxyiduronic acid,

the sodium salt of 1-(2,5-dich1orophenyl)-1-desoxy-guluronic acid,

the sodium salt of l,l-di-(2,5-dichlorophenyl)-l-desoxyguluronic acid,

the sodium salt of l-(2,5-dichlorophenyl)-l-desoxy-mannuronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-l-desoxymannuronic acid,

the sodium salt of 1-(2,S-dichlorophenyl)-1-desoxy-glucuronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-l-desoxyglucuronic acid,

the sodium salt of 1-(2,5-dichlorophenyl)-1-desoxy-a1- truronic acid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl)-1-des0xyaltruronic acid,

form or ethe .sodiumvsalt of 1-(2,5-dichlorophenyl)-1 desoxyalluronicacid,

the sodium salt of 1,1-di-(2,5-dichlorophenyl) -1-desoxyalluronic acid,

the sodium salt of lyxuronic acid,

the sodium salt of 1,I-di-(3,4-dichlorophenyl)-1-desoxylyxuronic acid,

the sodium salt of 1-(3,4-dichlorophenyl)-l-desoxyxyluronic acid,

the sodium salt of 1,l-di-(3,4-dichlorophenyl)-l-desoxyxyluronic acid,

the sodium salt of 1-(3,4-dichlorophenyl)-l-desoxyarabinuronic acid,

the sodium salt of 1,1-di-(3,4-dichlorophenyl)-l-desoxyar-ahinuronicacid,

the sodium salt of 1-(3,4-dichlorophenyl)-1-desoxyriburonic acid,

the sodium salt of 1,l-di-(3,4-dichlorophenyl)-l-desoxyriburonic acid,

the sodium salt of l-(3,4-dichlorophenyl)-l-desoxytaluronic acid,

the sodium salt of 1,1-di-(3,4-dichlorophenyl)-l-desoxytaluronic acid,

the sodium salt fgalacturonic acid,

1-(3,4-dichlorophenyl)-1-desoxyof 1-( 3,4-dichlorophenyl -1-desoxythesodium salt of 1,1-di-(3,4-dichlorophenyl)-1-desoxygalacturonic acid,the sodium salt of l-(3,4-dichlorophenyl)-l-desoxyiduronic acid, thesodium salt of 1,1-di-(3,4-dichlorophenyl)-1-desoxyiduronic acid,

the sodium salt of l-(3,4-dichlorophenyl)-1-desoxyguluronic acid,

'the sodium salt of 1,1-di-(3,4-dichlorophenyl)-1-desoxyguluronic acid,

,the sodium salt of 1-(3,4-dichlorophenyl)-1-desoxymannuronic acid,

"the sodium salt of 1,1-di-(3,4-dichlorophenyl)-l desoxymannuronic acid,a the sodium salt of 1-(3,4-dichlorophenyl)-1-desoxyglucuronic acid, thesodium salt of 1,1-di-(3,4-dichlorophenyD-l-desoxyglucuronic acid, thesodium salt of l-(3,4-dichlorophenyl)-l-desoxyaltruronic acid, thesodium salt of 1,l-di-(3,4-dichloropheny1)-l-desoxyaltruronic acid, thesodium salt of 1-(3,4-dichlorophenyl)-1-desoxyalluronic acid, the sodiumsalt of 1,l-di-(3,4-dichlorophenyl)-l-desoxy- 'alluronic acid.

:f Friedel-Crafts metal halide catalysts which are employed in modifiedby means of an alcohol, an ether, an ester, a nitroparafiin, etc. togive a catalyst of controlled -activity,i so desired. AFriedel-Craftsmetal halide catalyst which is preferred for use in thisprocess is substantially, anhydrous aluminum chloride. Other Friedel-Crafts metal halides which may be utilized as catalysts in this process,but not necessarily with equivalent results, are aluminum bromide,ferric chloride, ferric bromide, zinc chloride, beryllium chloride,gallium chloride, titanium tetrachloride, zirconium chloride, stannicchloride,tc.

Ihe' .process may be carried'out by slowly adding a Friedel Crafts metalhalide catalyst such as aluminum chloride to a stirred mixture of arylhalide and sugar acid lactone while maintaining the reaction temperatureat from about -20 C. to about 150 C., and preferably at from about 20 C.to about 100 C. After the reaction mixture has reached the desireddegree of reaction or completion, the entire reaction mixture andcatalyst may be mixed with water or may be added to ice in Order toquench the activity of the catalyst and to permit separation of theorganic reaction product and unreacted starting materials.

The nature of this invention is illustrated further by thefollowingexample, which however should not be construed to limit unduly thegenerally broad scope of the invention- EXAMPLE I A one liter glassalkylation flask, equipped with a mercury sealed stirrer and a refluxcondenser connected to a soda lime tower was charged with 25 grams ofglucuronolactone, 333 grams of chlorobenzene and grams of aluminumchloride. The flask was then heated on a water bathfor 4.5 hours at 7075C. during which time 22 grams of hydrogen chloride was evolved asmeasured by the increase in the weight of the soda lime tower. I

' The contents of the alkylation flask were then treated with ice todecompose the aluminum chloride remaining therein. Ether was added tothe system, making a homogeneous phase together with the product andexcess chlorobenzene. This phase was washed with water and evaporatedover steam to a dry solid weighing 59 grams and hereinafter designatedas product A. The aqueous washes were neutralized with sodium hydroxidesolution and evaporated to dryness. No organic residue was noted in thedry salt.

Segment A was placed in about 200 cc. of water, and solid sodiumhydroxide was added until the solution was definitely alkaline. This washeated to boiling, filtered (less than 5% remained insoluble), and thefiltrate kept at 1 0 C. for three days. At this point, a largeprecipitate of the sodium salt of the product had separated out in theflask. This solid product was filtered off and dried.

The sodium salt was then converted into the free acid product bydissolving the sodium salt in hot water, filtering, and then acidifyingthe filtrate with hydrochloric acid. The free acid separated as a lightyellow oil. This oil crystallized slowly over a period of 3-4 daysyielding more than 34 grams of lactone hereinafter designated as productB.

Data about the lactone, B, follows:

It could be crystallized from water in which its solubility was lessthan 0.1% at boiling point. The crystals were in the form of plateswhich, after drying at 25 0., had a melting point of 78-80".

Sesqulhydrate of dichlorophenyl-desoxyglucuronolactone.

These crystalline plates, upon drying at 98 C. lost Water and gave acrystalline material with melting point 108-110 C. analyzing as follows:

Percent Fennel--. 53.91 4.50 17.40 Caled. for CHHMOUJIQO" 53.88 4.517.68

Monohydrate of dlchlorophenyldesoxy-glucuronolactone.

Oxidation with chromic acid:

Chromic acid oxidation gave 4,4'-dichlorobenzophenone identified by itsmelting point and unchanged mixed melting point with pure referencecompound.

open-ore Elementary analysis I Pegzis'nt Found 1'4. 29 Calcd. forCraHnOeNfiCh. 4H v14. 32

. These data show that the following condensation oc curred in thepresence of AlCl The product is regarded as the lactone rather than asthe free acid of structure:

COOH

because of the high degree of water insolubility. A strucwill dissolve:in diluted sodium hydroxide to'lgive the sodium salt:

Sodium salt of 1,1-di- (p-chlorophenyl)-1-desoxyglueuronic acid Theobserved yield of 34 grams of the diarylated lactone was 60% of thetheoretical and represented an exceptionally high yield of a purereaction product.

Eight grams of the thus prepared1,1-di-(p-ch1orophenyl)-l-desoxy-glucuronolactone and six grams of themethyl ester of stearic acid are dissolved in m1. of dimethylformamideand the resultant mixture is heated to 100 C. About one gram of K 00 isadded and a vacuum of 100 mm. is applied to the system. Thesystem isstirred for six hours at 100 C. during which time about 1 gm. ofmethanol distills out. Stirring is stopped, and the dimethylformamide isdistilled out. The dry product, about 1'2 grams, is suitable for use asa nonionic detergent with germicidal properties. It can be built withsodimn tripolyphosphate to yield a foaming detergent, or utilized per sefor clothes washing.

We claim as our invention:

1. A compound selected from the group consisting ofhaloaryl-l-desoxy-alduronolactone, haloaryl-l-desoxy-alduronic acid, anda sodium salt of haloaryl-l-desoxy-zilduronic acid.

. Halophenyl-l-desoxy-alduronolactone.

. Halophenyl-l-desoxy-hexuronolactone.

. Chlorophenyl-l-desoXy-hexuronolactone.

l-(p-ohlorophenyl) -1-desoxy-glucuronolactone.

1 1 -di- (p-chlorophenyl -1-desoxy-glucuronolact0ne.Halophcnyl-1-desoxy-alduronic acid.

. Halophenyl-l-desoxy hexuronic acid.

. Chlorophenyl-l-desoxy-hexuronic acid. 7

10. '1-(p-chlorophenyl)-l-desoxy-glucuronic acid.

11. 1,1-di-(p-chloropl1enyl) -1-desoxy-glucuronic acid.

12. The sodium salt of halophenyl-l-desoxy-alduronic acid.

13. The sodium salt of acid.

14. The sodium salt of chlorophenyl-l-desoxy-hexuronic acid.

15. The sodium salt of l-(p-chlorophenyD-l-desoxyglucuronie acid.

16. The sodium salt of 1,1-didesoxy-glucuronic acid.

halophenyl-l-de'soxy-hexuronic (p-chlorophenylJ-l- References Cited inthe file of this patent UNITED STATES PATENTS 2,472,276 Bonner 'June 7,1949 2,798,098 Linn July 2, 1951 2,798,100 Linn July 2, 1957

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF HALOARYL-1-DESOXY-ALDURONOLACTONE, HALOARYL-1-DESOXY-ALDURONIC ACID, AND A SODIUM SALT OF HALOARYL-L-DESOXY-ALDURONIC ACID.
 5. 1-(P-CHLOROPHENYL)-1-DESOXY-GLUCORONOLACTONE. 